Oxide‐Derived Bismuth as an Efficient Catalyst for Electrochemical Reduction of Flue Gas

Abstract Post‐combustion flue gas (mainly containing 5–40% CO 2 balanced by N 2 ) accounts for about 60% global CO 2 emission. Rational conversion of flue gas into value‐added chemicals is still a formidable challenge. Herein, this work reports a β‐Bi 2 O 3 ‐derived bismuth (OD‐Bi) catalyst with surface coordinated oxygen for efficient electroreduction of pure CO 2 , N 2, and flue gas. During pure CO 2 electroreduction, the maximum Faradaic efficiency (FE) of formate reaches 98.0% and stays above 90% in a broad potential of 600 mV with a long‐term stability of 50 h. Additionally, OD‐Bi achieves an ammonia (NH 3 ) FE of 18.53% and yield rate of 11.5 µg h −1 mg cat −1 in pure N 2 atmosphere. Noticeably, in simulated flue gas (15% CO 2 balanced by N 2 with trace impurities), a maximum formate FE of 97.3% is delivered within a flow cell, meanwhile above 90% formate FEs are obtained in a wide potential range of 700 mV. In‐situ Raman combined with theory calculations reveals that the surface coordinated oxygen species in OD‐Bi can drastically activate CO 2 and N 2 molecules by selectively favors the adsorption of *OCHO and *NNH intermediates, respectively. This work provides a surface oxygen modulation strategy to develop efficient bismuth‐based electrocatalysts for directly reducing commercially relevant flue gas into valuable chemicals.